As a novel photocatalyst supporting material, one-dimensional hollow PAN nanofiber mat (HPAN) was successfully fabricated via coaxial solution blowing method (CSB), which we named CSB-HPAN. Then modified hollow PAN Fe complex (Fe-AO-CSB-HPAN) was prepared by the amidoximation and Fe coordination of AO-CSB-HPAN which used for the heterogeneous Fenton degradation of textile dyes. SEM, TEM and the digital photo revealed that CSB-HPAN has hollow structure, three-dimensional curly and loosely fibrous morphologies, which is beneficial for Fe³⁺ complexation, dye adsorption and degradation. The experiments of photocatalytic activity indicated that Fe-AO-CSB-HPAN showed excellent photocatalytic performance in the degradation of textile dyes in the presence of H₂O₂ under light irradiation. Meanwhile, 99% of RR195 molecules were decomposed by Fe-AO-CSB-HPAN in 35 min, which was faster than by conventional modified electrospinning PAN nanofiber Fe complex (Fe-AO-ES-PAN), due to the large surface area and loosely fibrous structure of Fe-AO-CSB-HPAN.